Process for breaking petroleum emulsions employing certain oxyalkylated triethylene tetramines



y 1960 I M. DE GROOTE ETTAL 2,94

PROCESS' FOR BREAKING PETROLEUM EMULSIONS EMPLOYING CERTAIN OXYALKYLATED TRIETHYLENE TETRAMINES Filed Aug.- 10, 1954 C4Ha0 FIG. 2 0 l0 c 22 I l2 TRIETHYLENE TETRAMINE C3H6 o I007. I 100/.

INVENTORS I butylene carbonate.

State PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN OXYALKYLATED TRIETHYLENE TETRAMINES Melvin De Groote, University City, and Owen H. liet-v fingill, Kirkwood, Mo., assignors to Petrolite Corpora- This invention relates to processes or procedures partrcularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that .are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase otthe emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions firom mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in reinovinig1 impurities particularly inorganic salts, from pipeme o More specifically then the present invention is concerned with a process for breaking petroleum emulsions employing a demulsifier including a cogeneric mixture of a homologous series of glycol ethers of triethylene tetramine. The cogeneric mixtures are derived exclusively from triethylenetetramine, ethylene oxide, propylene oxide and butylene oxide, in such weight proportions so the average composition of said cogeneric mixture in terms of the initial reactants lies approximately within the truncated triangular pyramid identified as E, H, F, I and G, J, in Figure l; with the proviso that the percentage of ethylene oxide, by weight, is. within the limits: of 2% to 39.5% and the remaining three initial reactants re:- calculated to 100% basis. lie approximately within the triangular area defined in Figure 2 by points 1 4, 6. However, as: will be pointed out subsequently the same ultimate compositions may be employed using any one of the three oxides last. The oxyalkylation oi:-triethyleneztetramine by means of ethylene. oxide, propylene oxide, or butylene oxide has been: described in the literature. One can. use instead of the oxides the corresponding alkylene carbonates, to wit, ethylene carbonate, propylene carbonate, or

As is well known, the oxyalkylation derivatives from any oxyalkylationrsusceptible compound, are prepared by the: addition reaction between such oxides and such compound. The addition reaction is advantageously carried out at an elevated temperature and pressure and in the presence of a small amount of alkaline catalyst. Usually, the catalyst is sodium hydroxide or sodium methylate. The reaction temperature is apt to be 140 C. or somewhat less, and'the reaction pressure not in excess of 30 to 50 pounds per square inch. The reaction proceeds rapidly. See, for example, U.S. Patent No; 2,636,038, dated April v21, 1953, to Brandner, although another hydroxylated compound is employed.

' As. to further. information in regard to the mechanical steps involved in oxyalkylation, see. U.S. Patent No.

atent Patented July 12,. 1960.

2 2,499,365, dated March 7, 1950, to De Grooteet a1. Particular reference is made to columns 92 et seq.

The oxyalkylation of a liquid or a solid which can be melted at comparatively low temperature (under 150 C.) without decomposition or is soluble in an inert solvent, such as Xylene, presents little or no mechanical diificulties in the oxyalkylation step; When one has a solid which cannot be melted, or decomposes on melting, and ,is insoluble in xylene, a slurry may be employed as in the case of the oxyalkylation of sucrose. See U.S. Patent No. 2,652,394, dated September 15, .1953, to 'De Groote. Actually, as far as oxyalkylating a slurry of a xyleneinsoluble solid in xylene the procedure is substantially the same for pentaerythritol, or sorbitol, or sucrose, or for that matter, for glucose, or a solid amine such as tris(hydroxymethyl)aminomethane.

However the oxyalkylation of a liquid amine and particularly a liquid polyamine, such as diethylene triamine, triethylene tetramine, tetraethylene pentamine, and higher polyethylene amines having 6, 7 or 8 nitrogen atoms as well as 3,3'-iminobispropylamine, represents a simpler procedure for the reason that one is using a liquid product in the initial step. A solvent could be readily added to such product or compound.

The oxyalkylation of an amine, particularly a primary amine, or secondary amine or a hydroxylated amine regardless of whether it is primary, secondary, or tertiary, is comparatively simple and has been described repeatedly in the literature.

If the product is a liquid, such as tn'ethano'lamine, one can proceed to treat with an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide, at least in the early stages if desired without adding any catalyst. Generally speaking, it oxyalkylation is rather extensive as in the present instance, one requires a cata lyst after the initial stage and it is just as simple to add it from the very beginning.

The oxypyropylation of a polya'rnine, such as triethylene tetramine, is comparatively simple because suchproducts or similar products are usually liquids at ordinary temperature and invariably at oxyalkylation temperatures Indeed, the procedure is simply to oxyalkylate without addition of any catalyst if desired, and then when oxyalkylation slows up add the usual basic catalyst, such as powdered caustic soda or powdered sodium methylate. If desired, such catalyst can beadded at the very beginning. It is also desirable in such cases where exhaustive oxyalkylation is concerned to add a diluent, such as xylene, high boiling petroleum solvent, or the like, at thevery beginning. Such solvents usually are miscible but if not miscible one obtains a suspension or temporary emulsion and as soon as oxyalkylation has proceeded toeven a slight degree the entire mass is homogeneous.

Specific reference is made to the instant application which is concerned with ethylene oxide and butylene oxide or the equivalents. Actually, Whether one uses ethylene oxide or butylene oxide or, for that matter, propylene oxide, one preferably starts with the amine or polyamine suspended in the form of a slurry, emulsion, suspension or solution. There would be a slurry in event the amine is a solid and insoluble. In the present case, however, the amine is a liquid as previously pointed out.

If desired, one can employ an alkylene carbonate, such as ethylenecarbonate, butylene carbonate, or proi pylene carbonate, for the initial oxyalkylation. such initial oxyalkylation has gone far enough to convert the polyarnine into a solvent-soluble product, i.e., soluble in xylene or an aromatic petroleumsolvent, one

can then use the oxides. The carbonates, of course, cost more than the oxides and there is'no real advantage in most cases unless one starts with an insoluble amine such here as tris(hydroxymethyl)aminomethane and this does not apply in the present case.

In any event, as is well known, the oxyethylation of polyamines proceeds just as readily as the oxypropylation and this applies also to oxybutylation, particularly if the straight chain butylene oxide isomers are employed. See, for example, U.S. Patents Nos. 2,679,511, 2,679,512, 2,679,513, 2,679,514 and 2,679,515, all dated May 25, 1954, to De Groote.

It is not believed any examples are necessary to illustrate such well known procedure but for purpose of illustration the following are included:

Example 1a The reaction vessel employed was a stainless steel autoclave with the usual devices for heating, heat control, stirrer, inlet, outlet, etc., which is conventional in this type of apparatus. The capacity was approximately 4 liters. The stirrer operated at a speed of approximately 250 rpm. There were charged into the autoclave 500 grams of triethylene tetramine, 300 grams of xylene, and '15 grams of sodium methylate. The autoclave was sealed, swept with nitrogen gas and stirring started immediately and heat applied. The temperature was allowed to rise to approximately 145 C. At this particular time the addition of butylene oxide was started. The butylene oxide employed was a mixture of the straight chain isomer substantially free from isobutylene oxide. It was added continuously at such speed that it was absorbed by the reaction as added. The amount added in this operation was 1500 grams. The time required to add the butylene oxide was two hours. During this period the temperature was maintained at 130 C. to 145 C., using cooling water through the inner coils when necessary and otherwise applying heat if required. The maximum pressure during the reaction was 50 pounds per square inch. Ignoring the xylene and sodium methylate and considering the triethylene tetramine for convenience, the resultant product represents 3 parts by Weight of butylene oxide to one part by weight of triethylene tetramine. The xylene present represented approximately .6 of one part by weight.

Example 2a Example 3a In a third step, instead of adding 1500 grams of butylene oxide, 1625 grams were added. The reaction slowed up and required approximately 6 hours, using the same operating temperatures and pressures. The ratio at the end of the third step was 9.25 parts by weight of butylene oxlde per Weight of triethylene tetramine.

Example 4a At the end of this step the autoclave was opened and an additional 5 grams of sodium methylate added, the autoclave flushed out as before, and the fourth and final oxyalkylation completed, using 1625 grams of hutvlene oxide, and the oxyalkylation was complete witliin 3% hours using the same temperature range and pressure as previously. At the end of the reaction the product represented approximately 125 parts of butylene oxide by weight to one part of triethylene tetramine.

All the examples, except the first step, were substantially water-insoluble and xylene-soluble.

As has been pointed out previously these oxybutylated triethylene tetramines were subjected to oxyethylation in the same manner described in respect to the oxypropylated glucose in aforementioned US. Patent No. 2,626,935. Indeed, the procedure is comparatively simple for the reason that one is working with a liquid and also that ethylene oxide is more reactive than butylene oxide. As a result, using the same amount of catalyst one can oxyethylate more rapidly than usually at a lower pressure. There is no substantial difference as far as operating procedure goes whether one is oxyethylating oxypropylated triethylene tetramine or oxybutylated triethylene tetramine.

The same procedure using a slurry of triethylene tetramine in xylene was employed in connection with ethylene oxide and the same mixture on a percentage basis was obtained as in the above examples where butylene oxide and triethylene tetramine were used.

The same procedures have been employed using other butylene oxides including mixtures having considerable isobutylene oxide and mixtures of the straight chain isomers with greater or lesser amounts of the 2,3 isomer.

Where reference has been made in previous examples to the straight chain isomer, the product used was one which was roughly or more of the 1,2 isomer and approximately 15% of the 2,3-cisand the 2,3-trans isomer with substantially none or not over 1% of the isobutylene oxide.

In the preceding procedures one oxide has been added and then the other. One need not follow this procedure. The two oxides can be mixed together in suitable proportions and subsequently subjected to joint oxyalkylation so as to obtain products coming within the specified limits. In such instances, of course, the oxyalkylation may be described as random oxyalkylation insofar that one cannot determine the exact location of the butylene oxide or ethylene oxide groups. In such instances the procedure again is identically the same as previously described and,- as a matter of fact, we have used such methods in connection with molten sorbitol.

If desired, one may add part of one oxide and all of the other and then return to the use of the first oxide, for instance; or one may use the procedure as previously, adding first some butylene oxide, then ethylene oxide and then the butylene oxide. Or, inversely, one may add some ethylene oxide, then all butylene oxide and then the remainder of the ethylene oxide; or either oxide could be added in portions so that first one oxideis added, then the other, then the first oxide is added again, and then the second oxide. We have found no advantage in so doing. Indeed, our preference has been to add all the butylene oxide first and then the required amount of ethylene oxide.

As pointed out previously, triethylene tetramme can be oxyethylated in the same way it is oxybutylated, i.e., by preparing a slurry in xylene or in a similar solvent and using a suitable alkaline catalyst such as caustic soda, sodium methylate, or the like, and then adding the ethylene oxide. The changes previously mentioned are of difference in degree only. In other Words, oxyethylation will take place at a lower temperature, for instance, a top temperature of probably to C. instead of to C. The same weight of ethylene oxide could be added in 75% to 85% of the time required for butylene oxide. The pressure during the reaction, instead of being 35 to 45 pounds as in the case of butylene oxide, is apt to be 10 to 15 pounds and at times a little higher. Otherwise, there is no difference.

Also, if desired, the use of ethylene carbonate is a very convenient way of oxyethylating triethylene tetramine. In fact, it can be oxyethylated without the use of pressure. Such procedure, and particularly melting the carbonate first and adding the triethylene tetramine slowly permits the production of a reaction mass which is a liquid or which melts readily at comparatively low temperatures to yield a liquid. Such reaction should be condllt lql in such a Way that there is no residual ethylene the massis transferred to an autoclave. In fact,,pro-

pylene carbonateis' more satisfactory than ethylene carbonate.

One can oxyalkylate using an acid catalyst or an alkaline catalyst or at least in part, without the use of any catalyst although such procedure is extremely slow. and uneconomical; In other words, any one of the conventional catalysts used in oxyalkylation may be employed. It is our preference, however, to mean alkaline catalyst such as sodium methylate, caustic soda, or the like. "Actually, triethylene tetram-inemay contain a trace of moisture. 'Our' preference is to prepare 'a mixture with an excess of'xylene and distill oil a part of the xylene so as to remove any trace of water and then flush out the mass'with nitrogen. Even so, there may be a few tenths of a percent of moisture remain although at times examination indicates at the most it is merely a trace. r

Actually, the, oxyalkylation of triet-hylene tetramine is comparatively simple because it is a liquid and if desired one could start without mixing the product with any solvent whatsoever. In procedures involving exhaustive oxyalkylation it is advantagwus to use-a solvent without regard to whether one obtains a solution, suspension, emulsion or slurry as has been pointed out previously; Indeed, one can use the same procedure as in the case of sorbitol in which there actually is a slurry tor the rea': son that sorbitol does not dissolve in xylene. ;See, for example, US. Patent No. 2,552,528 dated May 15, .1951, to De Groote wherein the product subjected to oxyalkyla .tion is sonbitol. When butylene-oxide is-used the same procedure can be followed as in the use of propylene oxide asdescribed in Example A inPart 2 .of the aforementioned U. S., Patent 552,528; or, if desired, butylene oxide can be used and the same procedure can be followed as in the use of propylene oxideas described in Example li of the aforementioned U.S.. Patent-2,626,-

.935. The triethylene tetramine is stirred with a solvent,

such as diethylether' ofdiethyleneglycol or, :for thatmatter one may use ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, .or tetraethyleneglycol dimethyl ether. As 'oxybutylation proceeds the reaction mass becomes a homogeneous mass.

Here, again, it should be emphasized that one starts with a liquid which is soluble in or suspends in any one of a number of available solvents such as xylene. Thus,

the procedure is even simpler than the use of a solid such as sorbitol. However, the procedure employed can be the same as employed with sorbitol with the. exception that in the initial state one does not get a slurry. For this reason from time to time reference is made to the procedure involving the oxyalkylation of sorbitol.

Referring momentarily to US. Patent No..2,552,528, the finely powdered sorbitol is reacted with butylene. oxide and as oxybutylation takes place the reaction mass becomes :a homogeneous liquid; For instance, referring to Example A, column 16 of aforementioned patent, we have used identically the same procedure starting with triethylene tetramine. Instead of using 1600 grams of propylene oxide, there was used 1800 grams of butylene oxide (mixed straight chain isomers).

In Example B, instead of using 1100 grams of the propylene oxide derived intermediate from Example A, pre-' ceding, there was used instead 1191 grams of the butylene i In Example D, instead of 743 grams of the propylene -oxide derived. intermediate from Example C, preceding,

there was used 831 grams of the butylene oxide derived intermediate. Instead of adding 637 grams of propylene oxide in this stage, there was added 717 grams of butylene oxide.

It will be noted at this stage the ratio of butylene ox ide to triethylene tetramine was approximately 100-to-l, and the amount of triethylene tetramine represents less than 3%, by weight, of the end product and the amount ofbutylene oxide represented-over 97%.

Example E was conducted in the samemanner except that the initial reactant was Example D, preceding, and instead of using 566 grams, there was used instead 628 grams of the reactant. Instead of adding 563 grams of propylene oxide, there was added instead 633 grams of butyleneoxide. A

In this last example, five grams of sodium methylate were added as a catalyst to speed up the final stage of reaction. Operating. conditions, such as temperature, time factor, etc., were substantially the same-as described in the corresponding Examples A, B, D, C, andE, in aforementioned U.S. Patent 2,552,528.

,It will be noted that in this final product approximatel 200 moles of butylene ,oxide were employed per mole of triethylene .tetramine. On a percentage basis, the products represented approximately 1% triethylene tetramineand 99% butylene oxide. a

All examples, except the first stage, were substantially water-insoluble and xylene soluble. Y

It is immaterial in what order the oxides are added to triet-hylene' tetramine, so as to obtain the herein described products. However, our preference isto add butylene oxide first, then propylene oxide, and then ethylene oxide. There are two advantages in so doing. The first advantage is that products obtained as far as the general average goes following this succession of oxidesappears' to give the mostyalua'ble product. Secondly, it is easier from a purely manipulative standpoint to oxybutylate tri' V torily.

oxide derived intermediate, Example A. Instead of uspreceding example, there was used instead 1271 grams of butylene oxide derived intermediate B. Instead of adding 1995 grams of propylene oxide in this stage, there was 7 added instead 2345 grams of butylene oxide. r

So far as the use of butylene oxide is concerned, we prefer to use the straight chain isomers. r

or a mixture of the two. i

. As noted previously, one can oxyethylate first and thenadd either one of the other two oxides, to wit, butylene oxide or propylene oxide. Similarly, one can add either ox- .ide first, that is, propylene oxide or butylene oxide, and then add ethylene oxide, followed by the addition of the other oxide. Also, as is obvious, one need not add all the ethylene oxide alone or all the butylene oxide alone or all the propylene oxide alone. One could make a mixture of either one of the two, or all three, and use such mixture or mixtures as an oxyalkylating agent. Furthermore, one can add a fraction of any particular oxide and then add the rest at a subsequent stage. This may be applied not only to a single oxide but also to two of the three, or all three, of the oxides employed.

For the purpose of resolving petroleum emulsions of the water-in-oil type, we prefer to employ oxyalkylated derivatives, which are obtained by the use of monoepoxides, in such manner that the derivatives so obtained have sufiicient hydrophile character to meet at least the test set forthin U.S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity. J a

invention in terms of the four components.

The above mentioned test, i.e., a conventional emulisification test, simply means that the preferred product though it is xylene soluble, for example, it may also be 1 water soluble to an equal or greater degree.

For purpose of convenience, what is said hereinafter will be divided into four parts:

Part 1 is concerned with the oxyalkylation of triethylene tetramine broadly so as to obtain products within the compositional limits of the herein described invention;

Part 2 is concerned with binary or tertiary products derived from triethylene tetramine and a single oxide, or tris(hydroxymethyl)aminomethane and two oxides, which may be looked upon as intermediate products. More conveniently, the binary compositions may be considered as subintermediates and the tertiary compositional products as intermediates, all of which will be plain in light of the subsequent specification. Such intermediates are reacted with one more component, for instance, ethylene oxide, to give the four-component product described in'Pa 1, prec d ng. Part 3 is concerned essentially with the oxyethylation of the intermediate described in Part2, preceding. Needless to say, if the intermediate were obtained by the use of ethylene oxide, then thefinal stage would involve introduction of propylene oxide or butylene oxide.

Part 4 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds.

PART 1 The present invention is concerned with a cogeneric mixture which is the end product of a reaction or reactions involving 4 reactants. Assuming completeness of reaction and based on a mathematical average, the final product is characterized most conveniently in terms of the 4 component reactants. This phase of the invention is described elsewhere in greater detail.

In representing a mixture or an end product derived from 2 components or 3 components, there is no difficulty as far as using the plane surface of an ordinary printed sheet. For example, a 3 component system is usually represented by a triangle in which the apexes represent 100% of each component and any mixture or reaction product in terms of the 3 components is represented by a point in the triangular area in which the composition is indicated by perpendiculars from such point to the sides.

Chemists and physicists ordinarily characterize a 4- component system by using a solid, i.e., a regular tetrahedron. In this particular presentation each point or apex represents 100% of each of the 4 components, each of the 6 edges represents a line or binary mixture of the 2 components represented by the apexes or points at the end of the line or edge. Each of the 4 triangles or faces represent a tertiary mixture of the 3 components represented by the 3 corners or apexes and obviously signify the complete absence of the 4th component indicated by the corner or apex opposite the triangular face.

However, as soon as one moves to a point within the regular tetrahedron one has definitely characterized and specified a 4-component mixture in Which the 4 components add up to 100%. Such a representation of a 4- component system is described in detail in US. Patent 2,549,438 to De Groote et al.

The invention will be described by reference to the accompanying drawings, which illustrate, in conventional graphical form, compositions used in accordance with the In the drawings, Figure 1 is a conventional tetrahedron in which 'resents 39.5% ethylene oxide.

a trapezoidal area is blocked out and which defines the scope of the invention. Figure 2 is a planar figure by which, having a fixed amount of one constituent, the other three may be determined. I

Referring now to, Figure 1, the composition represented by the block which is really a truncated triangular pyramid designated y E. H; I; d G. Bear in m n that the base of the truncated pyramid, that is, E, F, G, does not rest on the bottom of the equilateral base triangle. Point D represents ethylene oxide. The base triangle represents the three other components and ObVic ously 0% ethylene oxide. For purpose of what is said herein, the lower base of the truncated pyramid, E, F, G, is a base parallel to the equilateral triangle, but two units up, i.e., representing 2% of ethylene oxide. Similarly, the upper base of the truncated pyramid H, I, J, lies in a plane which is 39.5 units up from the base, to wit, rep- Specifically, then, this invention is concerned with the use of components in which the ethylene oxide component varies from 2% to 39.5% ethylene oxide. The problem then presented is the determination of the other three components, to Wit, butylene oxide, propylene oxide, and triethylene triamine.

A simplification of the problem of characterizing a 4- component system which enters into the spirit of the present invention is this: If the amount of one component is determined or if a range is set, for example, 2% to 39.5% of ethylene oxide, then the diiference between this amount and 100%, i.e., 60.5% to 98%, represents the amounts of percentages of the other three components combined, and these three components recalculated to 100% bases can be determined by use of an ordinary triangular graph.

Actually, as far as the limiting points in the truncated pyramid are concerned, which has been previously referred to in Figure 1 it will be noted that in the subsequent text there is a complete table giving the composition of these points for each successive range of ethylene oxide. In other words, a perfectly satisfactory repetition is available by means of these tables from a practical standpoint without necessarily resorting to the data of Figure 2.

Figure 2 shows a triangle and the three components other than ethylene oxide. These three components added together are less than 100%, to wit, 60.5% to 98%, but for reasons explained are calculated back to 100%. This point is clarified subsequently by examination of the tables. It will be noted that Figure 2 shows a triangle 1, 4 and 6, which represents the bases (top, bottom, or for that matter, intermediate) of the truncated pyramid, also the area in composition which is particularly pertinent to the present invention.

PART 2 As has been previously pointed out, the compositional limits of the herein described compounds are set by a truncated triangular pyramid which appears in Figure 1. It would be immaterial since the figure A, B, C, D, is a regular tetrahedron whether one considered A, B, C, as the base, B, C, D, as the base, A, C, D, as the base, or A, B, D, as the base. In order to eliminate repetitious description which is obvious in light of the examples included, we have selected A, B, C, as the base. Another reason for so doing is that the preference is to use ethylene oxide as the final component and this selection of A, B, C, as the base lends itself most readily to such presentation.

As has been suggested previously it is simplest to refer to Figure 2 and concern oneself with a 3-component system derived from triethylene tetramine, propylene oxide and butylene oxide. Such product can then be reacted with 2% to 39.5% of ethylene oxide based on the final composition so as to give the preferred examples of the instant invention.

Returningnow momentarily to the preparation of the 3-component' intermediate shown in Figure" 2, itisobvious thathardly any directions arerequired to the composition of the initial reactants based on thetriangle in the attached drawing, it will-be noted that'we'have-calculated the percentage of the three initial reactants for points 1 to'23, inclusive, so as to yield the intermediate derived from triethyl'enetetramine, propylene oxide, and butylene oxide. These points determine not only the triangle but also numerous points within thetriangle; Furthermore, the points are selected so the area is dividedlinto five parts. three. of which are triangles and two of which are four-sided figures. The triangles are defined by the points 1, 2 and 8; 2, 3 and 8; 5, 6, and 7;

and the four-sided figures by the points 3, 4, 'and 9 and finally 3,8, 7 and 9. V.

Note that these data are included in- Table I- immedi ately following:

TABLE I V p 7 to giyesathe intermediate, iiefl, the three compenent producti Note that aihinary intermediate the preparation of Part 11 can be prepared in any suitable manner involving 1 214 pounds oftriethylen'e tetramine and" 98.86 pounds of propylene oxide.

Referring nowto the tertiary mixture table, it is apparent that for point 1. triethylenetetramine and'propyl one Tetra.-

Percent Percent Percent Percent mm e aee es es moanee e a ee stea s a Note: the first column. gives. various points, on the boundary of. the triangle or within the triangle. Note the next three col'umnsrepresent the tertiary mixture corresponding to the initial reactants,v i.e., the itermediate. These values. represent percentages, by weight, of triethylene tetramine,,.butylene-oxide and propylene oxid'e; Thus, it is apparentthat one can select any particular point in Figure 2 and simply use the appropriate amount of oxide to obtainthe selected intermediate. For instance, in regard to point 1,, all that would'be necese sary. would be to mix'86.5 pounds of'propylene, oxide with 12.5 pounds ofibutyl'enet oxide and use the mixture to oxyalliylate one pound offtriethylenetetramine. Similarly, in Example 2,,one need only mix 63 pounds of propylene oxide with 36 pounds of butylene oxide and use the mixture. tooxyalkyl'ate one pound of tn! ethylene tetramine in a manner previously indicated.

Note that the fifth and sixth columns represent binary mixtures; for. instance, in regard to the variouspoints on. the trianglev and within the triangle we have calculated. the initialmixt-ure usingtriethylene tetramine and propylene oxide in the first place and. using triethylene tetramine and ethylene oxide in the second place; which could he employed for subsequent oxyalkylationxto give the particular composition required; Stated another way, we have calculated" the composition' for'the sub intermediates which, when reacted with the other oxide; propylene oxide orbutylene oxide 2.8'1hE'CE88? may he,

proportion ch64 pounds of such; mixture and 36- pounds of? butylene oxide togivethedesired 3-component prod not. This is. obvious fronr the data in regard to the tertlarymixtures;

Referring: now to columns 7 and 8, it is obvious one "could' producean oxybutylated trtiethylene tetramine and then subject it to reaction with propylene oxide.

Using this procedurein. regard topoint 1, it is obvious the mixtureis obtained by 7142" pounds of triethylene' tetramine and 92.58 pounds of hutylene oxide. This produce can then. be subjected to'- reaction with propylene oxide in the ratio of 1'3i5 pounds of the mixture is employ such conventional-oxyalk'ylation procedure to obtain products corresponding to-- the composition as defined. Attention is again directed to the-fact that one need not addthe entire; amount of either oxide at one tir'ne- 'but" that a small portion ofi one could be added and them another small portionof theother, and the process repeated.

1 For purpose of illustration", we have prepared exam- 11 ples three diiferent ways corresponding to the compositions of the so called intermediate in Figure 2. In the first series, butylene oxide and ethylene oxide were mixed; this series is indicated at 1a, 2a, 3a, through and including 23a; in the second series, which represents our preferred procedure, butylene oxide was used first, followed by propylene oxide. This series has. been indicated as 1b, 2b, 3b, through and including 23b. Finally, in the third series propylene oxide was used first, followed by .butylene oxide and the series identified as 10, 20, 3c,

through and including 23c:

TABLE II Composition Composition Composition where Butylwhere Propyl- Oomposition Corresponding where Oxides ene Oxide ene Oxide to following Point; are Mixed used first used first Prior to Oxyfollowed by followed by alkylation Propylene Butylene Oxide Oxide 1a 1b 10 2a 2b 20 3a 8b 3:: 4a 4b 40 5a 5b 5e 6a 6b 60 7a 7b 70 8a 8b 8e 9a 9b 90 10a 10b we 11a 11b 12a 12b 120 13a 13b 136 14a 14b 140 16a 15b 15c 16a 16b 160 17a 17b 17a 18a 18b 180 19a. 19b 190 20a 20b 20c 21a 21b 21a 22a 22b 220 23a 23b 28c The products illustrated by the preceding examples are not, of course, the final products of the present invention. They represent intermediates. However, such intermediates require treatment with ethylene oxide to yield the product of the present invention.

PART 3 In Part 2 preceding there has been described the preparation of sub-intermediates and intermediates. As previously noted, these intermediates need onlybe subjected to conventional oxyethylation to produce the products described in the present invention. The amount of ethylene oxide employed is such that the final composition conforms to the composition set forth in Figure 1. This means that the amount of ethylene oxide used as a reactant represents 2% to 39.5% of the final product with the proviso that the remainder of the product is represent ed by the three remaining components within the proportions set forth in Figure 2.

In preparing examples we have done nothing more except use conventional oxyethylation, using an alkaline catalyst such as powdered caustic soda or sodium methylate. We have operated at temperatures varying from 110 C. to 135 C. We have used oxyethylation pressures of 10 pounds per square inch up to pounds per square inch, but usually not over 15 pounds per square inch. The time period has varied from 15 minutes when just a small amount of oxide was employed up to as much as 4 to 6 hours when a larger amount of oxide was used.

Obviously the simplest ofcalculations is involved although we have given the data in tabular form for the reason that we have indicated that the product containing 2% of ethylene oxide carries the designation A; the one having 5% ethylene oxide carries thedesignation B;

the one having 10% ethylene oxide is C; the one having v15 is D; the one having 20% is E; and the one having 25 is F. Similarly, designations G, H, I, J, K, and L are products containing 27.5% to 39.5% of ethylene oxide, respectively, as shown in Table III.

TABLE III [Proportions by weight] 3-Compo- Ethylene nent Inter- Ex.No. Oxide mediate of Designation Part 2, Preceding 2 98 A. 3 97 4 96 5 95 B. 6 94 7 93 8 92 9 91 I 10 90 C. 11 89 12 88 13 87 14 86 15 85 D. 16 84 17 83 18 82 19 81 20 E. 21 79 22 78 23 77 24 76 25 76 F. 27.5 72.5 G. 30.0 70 H. 32.5 67.5 I. 35.0 65 J'. 37.5 62.5 K. 39.5 60.5 L.

Since it would be impossible to prepare all the variants which have been previously suggested, we have pro ceeded as follows: We have prepared 30 examples corresponding to the 23 points in Figure 2 by varying the amount of ethylene oxide from 2% to 39.5%. One

example we have used 2%, another 5%, another 10%,

another 15%, another 20%, and another 25%, and on up to 39.5%, as shown. The intermediates used are those described in Table II, preceding. The prepared products have been described as follows: A-1a, B-2b, C-3c, D-4a, etc. A-la is, of course, the product obtained by using 98% of intermediate la previously described in Table II, and 2%, by weight, of ethylene oxide; Example B-Zb is obviously obtained by reacting 95%, by weight, of intermediate 2b with 5 by Weight, of ethylene oxide. Example C3c is obtained by reacting 90%, by weight, of intermediate Be With 10%, by weight, of ethylene oxide. Example D-4a is obtained by reacting of intermediate 4a with 15%, by weight, of ethylene oxide. 'Example E-5b is obtained by reacting 80% of intermediate 5b with 20%, by weight, of ethylene oxide. Example F-6c is obtained by reacting 75% of intermediate 60 with 25% of ethylene oxide.

It will be noted that the last series of 7 examples in Table IV are concerned with compositions corresponding to' points i, 5, 10, 15, 16, 20 and 23 in Figure 2. In these instances the compound having the F designation has 25% ethylene oxide; the one with a G designation has 27%.%; the one with the H designation, 30%; the one with the I designation, 32 /z%; the one with the J designation, 35%; the one with the K designation, 37Vz%; and the one with the L designation, 39 /z%. Note that in one instance the table shows all three types of preparation, that is in the instance of 116a, J 16b, and I160. The remaining examples in Table IV, following, are self-explanatory.

am ss TABLE IV Composition Gomposition Composition where xwhere Butylwhere Progyl GornpositionQorrespondides arev one Oxide. ene Oxl e. ing to tollowmg Point. Mixed Prior used first used first to Oxyalkylfollowed by followed by stion Propylene: Butylene Oxide Oxide A-la 1b 10 2a 3-2!) 20 3a' 3b 0-30 D-4a 4b 40 5a E-5b 50 6a 6b F-fic A-7a 7b 7c 80. 13-8!) 80 9o 9b 0-9: D-lOa 10b 101: 11a- E-llb 110 12a 12b. F.-12c A-13a 13b 130 1411 13-14!) 146 15a 15b Crlfid D-lfiiz 161; 16c 17c E-17b 170 18th 18b F480 A 19u 19b 190 2011 13-201) 200 21a 21b C.-21'c D-22a. 22b 220 23a E-23b' 23c la 1!) E-'-1c G-5a. 7 5b 50 10b ET-10b 100 16a 15b. 1 15c J'.16a .T-l6b J-16c a K 201)? 20a 23a 23b. L-23c The same: procedures have-been employed using 'other butylene: oxides. including; mixtures having considerable isobutylene oxide and mixtures of the straight chain isomers with; greater or lesser amountof the:2;3'isomer;

Where reference; has been made in previous examples to; the-straight. chain isomer, the: product used was one whichwas'roughly- 85% or more of the 1,2 isomer and approximately 15% of the 2,3-cisand the 2,3-trans isomer. with: substantially none. ornot over' 1% of the isobutylene oxide.

Indie-preceding procedures one oxide has-been added and then. the other. One need not follow this: procedure; The three oxides can be mixed together in suitable proportions andisubsequently subjected: to joint oxyalkylatioir so: as to obtainproducts coming Within the specified limits. In such instances;. of.course, the oxyalkylation maybe described'as random oxyalkylation insofar that one cannotzdetermine the exact location of the butylene oxide, propylene oxide or ethylene. oxide groups; In such instancesthe. procedure again is: identically the-same as-previously. described; and, as a matter of fact, wehave used such methods inconnection with triethylene-tetramine-.

If desired; one may addipart of: one oxide: andthen all the others and then return to the use. of the first oxide. For example, onemight use the procedure previously suggested, adding some butylene oxide, all" thepropylene oxide, all the. ethylene oxide; and then the remainder of the butylene oxide. Or, inversely, one. may-addsome propylene. oxide, then all the butylene oxide, then the remainder. of the propylene oxide, and then the ethylene oxide; Or, any one of the three oxides. could be. added in portionsso one oxide is added first, then the other two, thenthe first oxide is added. again, then the: other two. We. have found no advantage in. so doing; indeed, ounpreference has been to .add. all. the butylene oxide first, then. all the propylene oxide, and then the required amount of ethylene oxide.

As previously pointed out, triethylene tetramine can be oxyethylated in the same way it is oxybutylated, i.e., by heating the triethylene tetramine, using a suitable catalyst, particularly an alkaline catalyst, and adding the ethylene oxide. The changes previously mentioned are of diflerence in degree only. In other words, oxyethylaticn will take place at a lower temperature for instance,

a top temperature of: probably 110 to?1'-35"C;' instead'of 145 to 150 C; The same weight of ethylene oxide could" be added in to of the time required for butylene oxide. Thepressure during the reaction, instead ofbeing. 20 fto 35'pounds1asiin the case of'butylene oxide, is apt to be 10 to 30 pounds and at times a; little higher, but'fi'equently. operated at 15 pounds: per. square inch or less. Otherwise, there is no difference; Note, however, that it is easier and preferable to oxyethylate last, i.e., have a liquid reaction product'obtained by the use of butylene oxid'e'or'propylene oxide, for a combination of the two before the oxyethylation step.

Also, if desired, the use" of'ethylene carbonate is a very' convenient way of oxyethylating. triethylene tetramine. Intact, it canbe oxyethylated without thesusetof pressure.

One, can. oxyalkylate using an acid. catalyst or. amalkalinecatalyst or atleastin; part, withoutthe. use=of any catalyst although such: procedure: is extremely slow and uneconomicalL. In other Words, any one of the conven:- tional catalysts usedin: oxyalkylation. may be employed. It is: our preferencehowever, to. use an alkaline: catalyst such as sodium. methylate, caustic soda, or'the-like;

Actually,. triethylene; tetramine may contain 1%,. or somewhat: 1ess, of:water. When such compound is :heated to to and. subjected to vacuum, particularly when anhydrous nitrogen is. passed through. the: heated mass, the: resultant product appears to. becomesubstam tiallyi water free; Even: so,.there may. be. a.few:'t'enths:iof a; percent andperhaps only a trace .of'water remaining. in some instances;

Theproducts obtained by the above procedure usually show sometcolor varyingfr'omalight: amberi to aipale straw.. They canebe bleached inthe: usual fashion,.using bleaching clays, charcoahoran organic bleach, such. as peroxide-01' peracetic acid, or the like.

Such. products. also have present a small? amount of alkaline. catalyst: which can be removed? by: conventional means, or they can be neutralized by adding an equiv alentamount of acid, such as. hydrochloric acid. For many purposes the slight amount of residual; alkalinity is not objectionable.

Thereare certain variants which canbe employed without detracting fronrthemetes. and bounds'of'the. invention, butfor allv practical purposesthere is. nothing to be gained: by such variants and the result is; merely increased cost. For instance, anyone. of the two* oxides can bereplaced' to a. minor percentage andf'usuallyto' a very small degree, by oxide which would introduce: sub stantially the. same group along: with a side chain, for instance, one could' employ glycidyl methyl ether, glycidylf ethyl" ether, glycidyl isopropyl ether, glycidyl butyl ether or theilike.

Increased branching also may be effected by the use of an' imine instead of'a glycide, or awmethyl glycide;

ln thehereto appended claimsreference has been made to glycol ethers of triethylene tetramine)? Actually, it

will may be that the products shouldbe referred to as polyol ethers of triethylene tetramine" in order to emphasize the fact that'the final products of reaction have more than two hydroxyl radicals. However, the products may be considered as hypothetically derived by reaction of triethylene tetramine with the glycols, such as ethylene glycol, butylene glycol, propylene glycol, or polyglycols.

For this reason there seems to be a preference to use the terminology glycol ethers of triethylene triamine.

Attention again is directed to what has been said previously, to wit, that the four reactants as exemplified by the truncated triangular pyramid E, F, G, H, I, J, in the regular tetrahedron, A, B, C, D, as shown in Figure 1, might just as well be presented from any other position; that is, a position in which A, C, D, or B, C, D, or A; B, D, happened to be the base instead of A, B, C. However, such further elaboration would add nothing to what has been said previously and is obviously omitted for purpose of brevity.

PART 4 As to the use of conventional demulsifying agent reference is made to U.S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and eflfect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column'lS and ending in column 18, reference should be to Example J-16b, herein described.

Having thus described our invention, what we claim as new and desire to obtain by Letters Patent is:

l. A process for breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of triethylene tetramine; said cogeneric mixture being derived exclusively 'from triethylene tetramine, butylene oxide, propylene oxide and ethylene oxide in such weight proportions, so that the average composition of said cogeneric mixture stated in terms of the initial reactants, lies approximately within the truncated triangular pyramid identified as E, H, F, I, G and J in Figure 1, with the proviso that the percentage of ethylene oxide is within the limits of 2% to 39.5%, by weight, and the remaining three initial re- 'actants recalculated to 100% basis, lie approximately within the triangle defined in Figure 2 by points 1, 4 and 6.

2. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

3. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first.

4. The process of claim 1 with the proviso that oxyialkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide is substantially free from isobutylene oxide.

5. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide consists of 85% or more of the 1,2-isomer and approximately '15 or less of the 2,3-isomeric form, and is substantially free from isobutylene oxide.

6. The process of claim 5 with the proviso that the reactant composition falls Within the triangle defined by points 1, 2 and 8 in Figure 2.

7. The process of claim 5 with the proviso that the reactant composition falls within the triangle defined by points 2, 3 and 8 in Figure 2.

8. The process of claim 5 with the proviso that the reactant composition falls within the four sided figure defined by points 8, 3, 9 and 7.

9. The process of claim 5 with the proviso thatthe reactant composition falls within the four-sided figure defined by points 3, 4, 5 and 9.

10. The process of claim 5 with the proviso that the reactant composition falls within the triangle defined by points 5, 6 and 7.

11. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of triethylene tetramine; said cogeneric mixture being derived exclusively from triethylene tetramine, butylene oxide, propylene oxide and ethylene oxide in such weight proportions so that the average composition of said cogeneric mixture stated in terms of the initial reactants, lies approximately within the truncated triangular pyramid identified as E, H, F, I, G and J in Figure 1, with the proviso that the percentage of ethylene oxide is within the limits of 2% to 39.5%, by weight, and the remaining three initial reactants recalculated to 100% basis, lie approximately Within the triangle defined in Figure 2 by points 1, 4 and 6; with the proviso that the hydrophile properties of said cogeneric mixture in an equal weight of xylene, are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

12. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

13. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first.

14. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide is substantially free from isobutylene oxide.

.15. The process of claim '11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide consists of or more of the 1,2-isomer and approximately 15% or less of the 2,3-isomeric form, and is substantially free from isobutylene oxide.

16. The process of claim 15 with the proviso that the reactant composition falls within the triangle defined by points 1, 2 and 8 in Figure 2.

17. The process of claim 15 with the proviso that the reactant composition falls within the triangle defined by points 2, 3 and 8 in Figure 2.

18. The process of claim 15 with the proviso that the reactant composition falls within the four-sided figure defined by points 8, 3, 9 and 7.

19. The process of claim 15 with the proviso that the reactant composition falls Within the four-sided figure defined by points 3, 4, 5 and 9.

20. The process of claim 15 with the proviso that the reactant composition falls within the triangle defined by points 5, 6 and 7.

References Cited in the file of this patent UNITED STATES PATENTS 2,233,383 De Groote et al Feb. 25, 1941 2,457,634 Bond et al Dec. 28, 1948 2,549,438 De Groote et al. Apr. 17, 1951 2,552,530 De Groote May 15, 1951 2,574,544 De Groote Nov. 13, 1951 2,589,200 Monson Mar. 11, 1952 2,622,099 Ferrero et al. Dec. 16, 1952 2,649,483 Huscher et al. Aug. 18, 1953 2,677,700 Jackson et al. May 4, 1954 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO A DEMULSIFYING AGENT INCLUDING A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF TRIETHYLENE TETRAMINE, SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM TRIETHYLENE TETRAMINE, BUTYLENE OXIDE, PROPYLENE OXIDE AND ETHYLENE OXIDE IN SUCH WEIGHT PROPORTIONS, SO THAT THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE STATED IN TERMS OF THE INITIAL REACTANTS, LIES APPROXIMATELY WITHIN THE TRUNCATED TRIANGULAR PYRAMID INDENTIFIED AS E, H,F,I,G AND J IN FIGURE 1, WITH THE PROVISO THAT THE PERCENTAGE OF ETHYLENE OXIDE IS WITHIN THE LIMITS OF 2% TO 39.5%, BY WEIGHT, AND THE REMAINING THREE INITIAL REACTANTS RECALCULATED TO 100% BASIS, LIE APPROXIMATELY WITHIN THE TRIANGLE DEFINED IN FIGURE 2 BY POINTS 1,4 AND
 6. 